Method of controlling fungi with n-thio-monofluoro-dichloro-methyl imides



, are known already page 21). When the nitrogen atom United StatesPatent 3,341,403 METHOD OF CONTROLLING FUNGI WITH N- THIO MONOFLUORODICHLORO METH- YL IMIDES Erich Klauke, Cologne-Flittard, Engelbert Kuhleand Ferdinand Grewe, Cologne-Stammheim, and Helmut Kaspers and RichardWegler, Leverkusen, Germany, assignors to Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany, a corporation of Germany NoDrawing. Original application Oct. 31, 1961, Ser. No. 148,845, nowPatent No. 3,285,929, dated Nov. 15, 1966. Divided and this applicationMay 31, 1966, Ser. No. 553,663 Claims priority, application Germany,Nov. 3, 1960, F 32,468; Nov. 25, 1960, F 32,620 12 Claims. (Cl. 16730)This application is a divisional application of Ser. No. 148,845, filedOct 3|1, 1961, now US. Pat. No. 3,285,929.

The present invention relates to new and useful improvements infungicidal preparations and more particularly to improved fungicides.This invention also relates to methods of protecting organic materialsubject to attack by low orders of organisms. This invention furtherrelates to the synthesis of new chemical compounds, namelyN-thiomonofluoro-dichloromethyl imides of the following general formulain which X stands for organic acyl radicals and Y stands for anotheracyl radical or another suitable organic radical; X and Y may be linkedtogether, too, to form a common ring system.

Similar compounds of the aforementioned type which contain instead of an=NSCFCl -gr0up the =NSCCl -group from the literature. US. Patents 2, 72,553,772, 2,553,773, 2,553,774, 2,553,775, 2,553,776, 2,844,628, forinstance, describe a large number of such compounds containing atrichloromethyl-.mercapto group.

In accordance with the present invention it has now been found that alarge number of organic compounds containing the =NSCFCl -group areextremely effective for controlling the growth of fungi, and in thisrespect are superior to those compounds of the prior art containing the=NSCCl -group.

The physiologically active compounds of this invention may thus best berepresented as having the =NSCFCl -group etc. (see Hackh, ChemicalDictionary, second edition,

of the =NSCFCl -group Sidgwicks Organic Chemistry of Nitrogen, 1937edition, =pages 136 and 152).

3,341,403 Patented Sept. 12, 1967 Suitable amide compounds of'theindicated type are thus illustrated in Formula I:

(I) RX-1?ISOFC'1:

in which R represents an organic residue, possibly linked to X vianitrogen, oxygen or sulfur, too, X is part of an acyl group, such as forexample and R represents an organic radical or a hydrogen radical.Suitable imide compounds of the indicated type are illustrated byFormula II:

in which R represents one or more organic residues and X is part of anacyl group, such as for example (III) This reaction is shown only toillustrate this invention and not intended to limit it in any way. Otherinventive compounds as it may be seen from the examples can be preparedby exactly the same method.

The reaction to prepare the inventive compounds may be carried out atroom temperature or at slightly elevated temperature either in anaqueous medium or also in inert organic solvents such as benzene,dioxane, carbon tetrachloride and the like. If the free imides are used,i.e. if M stands for hydrogen, the reaction is carried out withpreferably in the presence of acid-binding agents, such as alkali metalhydroxides, -carbonates, -alcoholates, and the like, or also in thepresence of tertiary organic amines.

Starting materials for the inventive reaction broadly may be seen fromthe patent specifications mentioned at the beginning. As some examplesof the specifications there may be mentioned: phthalimide,tetrahydrophthalimide, 3.6-endomethylene-A -tetrahydrophthalimide, 3-nitrophthalimide, succinic imide, 2.4-dioxothiozalidine, parabanic acid,1.4-dioxyphthalazine, benzene sulfonic acid methylamide,4+chlorobenzene-sulfonic acid anilide, chloromethane sulfonic acidanilide or N.N.N.-trimethylsulfamide.

Another method suitable for the preparation of the inventive compoundsconsists in reacting the thio-trichloromethylamides known from theaforementioned specifications, with anhydrous hydrogen fluoride. Mostsurprisingly under even severe reaction conditions only one chlorineatom is split off and replaced by fluorine. The following reactionscheme may illustrate this method:

The two bonds before the nitrogen atom may preferably stand for theradical mentioned in the foregoing description.

Anhydrous hydrogen fluoride in the meaning of the above said statementshould be a commercial product with a content of about 2% of water, butpreferably not more.

The reaction usually is carried out under commercial pressure and attemperatures between and 20 C.; preferably anhydrous hydrogen fluorideis used in an excess so that it serves at the same time as a diluentdoes. The excess easily can be removed then by distillation. Of course,also other inert solvents may be used as diluents. These inert solventspreferably are nitrobenzene, diethylether, dioxane and the like.

The new inventive compounds as stated above are valuable pesticides withespecially fungicidal action and should be used in the field of plantprotection. The main advantage of the inventive compounds over thetrichloro compounds of the prior art is their better tolerableness onplants especially regarding phytotoxicity, without decreasing infungicidal activity. A further advantage over the prior art compounds isa longer lasting activity and better stability.

From the following experiment there is to be seen the high initialactivity of the inventive compounds. The test is a green-houseexperiment and has been carried out with tomato plants (Bonny Best).Aqueous emulsions of the .compounds shown in the table below have beensprayed on the plants. The aqueous emulsions have been prepared byadmixing the active ingredient with the same amount of dimethylformamide and a commercial nonionic emulsifier (NPlO). Plants sprayedwith these solutions are inoculated after 24 hours with zoosporangia ofPhytophthora infestans, and placed in humidity chambers at a temperatureof 20 C. and a relative humidity of 100%. They are kept there for 5days. After that the infestation has been checked and is shown in thetable below in comparison to an untreated control test, infestation ofwhich is set as 100.

Degree of infestation at a cone. of active ingredient in percent(aqueous emulsion) NSCFCh 0 5 NSOiN-SCFO12 0 3 H3O CuHs /NSOO13 3 14 C 0NSOqNSCCla 1 13 H30 CuHs Control 100 EXAMPLE 1 18.5 grams of thepotassium salt of phthalimide are dissolved in 100 ml. of toluene andtreated with a solution of 17.0 grams of dichlorofiuoromethane sulfenicacid chloride in 50 ml. of toluene at room temperature. Thereby thetemperature rises to about 40 C. Heating is continued for about half anhour at C., the reaction mixture then is filtered off the potassiumchloride. The crystal obtained is filtered off with suction. Afterrecrystallization from alcohol there are obtained 9 grams ofN-dichlorofluoro-methylthiophthalimide of M1. 152-152.5 C.

EXAMPLE 2 20 grams of N.N.dimethyl-N-phenylsulfamide and 17 grams ofdichlorofiuoro-methane sulfenic chloride are dissolved in ml. of tolueneand treated with 11 grams of triethylamine at room temperature. Therebythe temperature rises to about 40 C. After stirring for some time wateris added, the toluene layer is dried over sodium sulfate andconcentrated in vacuum. The crystalline residue melts afterrecrystallization from alcohol at 112 C. There are obtained 18 grams ofthe N.N-dirnethyl- N'-phenyl-N-dichlorofiuoromethyl-thiosulfamide.

In analogous manner there may be obtained the compounds of the followingformulae:

EXAMPLE 3 38 grams of A -tetrahydrophthalimide together with 10 grams ofcaustic soda are dissolved in ml. of Water and treated with 43 grams ofdichlorofluorornethane-sulfenic acid chloride at a temperature of 13-15C. The crystal mass obtained is after stirring for some time filteredoff with suction and washed with water. TheN-dichlorofiuoromethyl-thio-tetrahydrophthalimide melts at 102104 C.

5 6 In analogous manner there are obtained the compounds MP, C of thefollowing formulae:

H NsoFoh M.P. 46-48" 0. I

CICHZ SO2N-SCFCIQ M.P. 95 0. Bio-co 10 I /NSCFCh M.P. 82-84 0. 320-00Nsonon M.P. 126-128" 0. EXAMPLE 5 Into a suspension of 5 grams of thepotassium salt of so phthalimide in 100 ml. of dioxane there are addeddrop- 0 wise 5 grams of fiuorodichloro-methane-sulfenic bromide 115mgB.P. 24-27 C.), whereby the temperature of the mix- 8 1 3 ture rises toabout 30 C. After the addition of water N UPC 2 there are obtained 5grams of N-(dichloro-fluoro-methyl- Htoiofi thio-)phthalimide of M.P.152 C.

25 EXAMPLE 6 37 grams of furfurylidene-benzene-sulfonyl-hyd11azonEXAMPLE 4 together with 6 grams of sodium hydroxide are dissolved 1n 200ml. of water and this solution is treated with 26 46.6 grams of benzenesulfanilide together with 8 grams grams of fiuoro-dichloromethanesulfenic acid chloride of caustic soda are dissolved in 150 -ml. ofwater and are 30 at 15 to 20 C. Thereby crystallization of the mixturetreated dropwise with 34 grams of dichlorofluoromethaneoccurs. Thereaction mixture is stirred for some time and sulfenic acid chloride at1540 C.; the separated crystals the crystals are then filtered off withsuction. M.P. 100 are filtered off with suction and theN-thiodichlorofluoro- 103 C. Yield: grams.methyl-N-phenyl-benzene-sulfonic acid amide is crystal- In analogousmanner there are obtained the compounds lized from methanol; M.P.116-120 C. 35 of the following formulae:

-SO2I}IN=CH M.P. s7-91 o.

SOFClr SO;IIIN=OH--Ol M.P. 121-123 o.

SOFCI:

In an analogous manner there are obtained the com- EXAMPLE 7 pounds ofthe following formulae:

A solution of 26.8 grams of the cyclic sodium salt of I Q (011) Iimalei-c acid hydrazide in 200 m1. of water is treated dropwise with 34gram-s of fiuoro-di-chloro-methane sulfenic C1 y acid chloride, at atemperature of 10 to 12 C. Thereby a V i crystal mass is obtained, whichafter stirring the mixture 1- -80 NSCFCI M.P. 52 0. p C Q 6 2 for sometime is filtered off with suction. There are oh- 3 tained 37 grams ofthe corresponding sulfenic acid deriva- OflN tive of M.P. 205210 C.(under decomposition). ci--son scroh M.P. 58 0.

CH3 EXAMPLE 8 H3c-soi A mixture of 11.7 grams ofthiazo1ine-l.3-dione-(2.4) gp h and 4 grams of sodium hydroxide isdissolved in 100 m1. of sC-SbzNSCFCl: M.P. 136 0. water and thissolution is treated with 17 grams of fluorodichloro-methane sulfenicacid chloride at a temperature 'of 10 to 15 C. The separating crystal(21. grams) is filtered off with suction and dried; M.P. 49 to 52 C.

In analogous manner there are obtained the compounds of the followingformulae:

In to a reaction container, of copper or of stainless steel and providedwith a stirrer, a reflux condenser and a thermometer, there are placed15 grams of N-trichloromethyl-thiophthalimide. Under anhydrousconditions there are added to this solution about 100 grams of anhydroushydrofluoric acid at a temperature of about C. This mixture is now afterstirred for 65 hours while the temperature rises slowly. During thereaction the reflux condenser is cooled with NaCl-ice water andprotected against air-humidity with a CaCl -tube. The mixture afterwardsis poured on 400 grams of ice and the separated residue is filtered offwith suction. After washing thoroughly with water there are obtained13.5 grams of N-dichloro-fluoromethyl-thiophthalimide of M.P. l5015l C.(from alcohol).

Analysis.C H Cl FNO S.--Calculated: F, 6.78%. Found: F, 6.60%.

We claim:

1. A method of controlling fungi which comprises contacting fungi with afungicid-ally effective amount of a compound having the formula orR1TISCF wherein R is selected from the group consisting of an aliphaticradical, an aromatic radical and a heterocyclic radical and R is anorganic acyl radical linked to the nitrogen through the acyl portion.

3. A method according to claim 1 wherein the com pound has the formulawherein X is an acyl radical and R is selected from the group consistingof an aliphatic, an aromatic and a heterocyclic radical.

4. A method according to claim 1 wherein the compound has the formula 0NSCFClz ll 0 v 5. A method according to claim 1 wherein the compound hasthe formula HaC\ NSOzIIISC F C12 H3O Co 5 6. A method according to claim1 wherein the com pound has the formula HaC-SOz-IIISC F C12 7. A methodaccording to claim 1 wherein the compound has the formula 8. A methodaccording to claim 1 wherein the compound has the formula N-SOa-N- 8-0 FC1:

NSCFCh II 10. A method according to claim 1 wherein the compound has theformula NSOFCI:

NS Oz-N-SCF C12 9 10 12. A method according to claim 1 wherein the com-References Cited pound has the formula CH3 UNITED STATES PATENTS \NSOr-NSCF 01, 2,553,770

5 5/1951 Kittleson 260326 XR g 2,553,771 5/1951 Kittleson 260326 ALBERTT. MEYERS, Primary Examiner. 1 DALE R. MAHANAND, Assistant Examiner.

1. A METHOD OF CONTROLLING FUNGI WHICH COMPRISES CONTACTING FUNGI WITH AFUNGICIDALLY EFFECTIVE AMOUNT OF A COMPOUND HAVING THE FORMULA